US4831078A - Process for producing copolymer latex - Google Patents

Process for producing copolymer latex Download PDF

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Publication number
US4831078A
US4831078A US07/220,394 US22039488A US4831078A US 4831078 A US4831078 A US 4831078A US 22039488 A US22039488 A US 22039488A US 4831078 A US4831078 A US 4831078A
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Prior art keywords
weight
parts
molecular weight
modifier
monomer
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US07/220,394
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English (en)
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Kohichi Kuhara
Takahiro Shimazoe
Toshiro Ishizuka
Masayoshi Sekiya
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Zeon Corp
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Nippon Zeon Co Ltd
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Assigned to NIPPON ZEON CO., LTD., A CORP. OF JAPAN reassignment NIPPON ZEON CO., LTD., A CORP. OF JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ISHIZUKA, TOSHIRO, KUHARA, KOHICHI, SEKIYA, MASAYOSHI, SHIMAZOE, TAKAHIRO
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers

Definitions

  • This invention relates to a copolymer latex suitable for use as a binder in a paper coating composition having good blister resistance and print gloss.
  • Pigment-coated paper using a copolymer latex as a binder has various excellent properties such as whiteness, gloss, water resistance and adhesion strength, and therefore has been used in increasing amounts with the wide-spread use of offset rotary presses.
  • Blister resistance is one important property required of copolymer latices used in coated paper for offset rotary printing.
  • One known method of improving the blister resistance is to control the amount of a gel in the copolymer latex (U.S. Pat. No. 3,970,629).
  • the amount of the gel is decreased by simply increasing the amount of the molecular weight modifiers used, the blister resistance of the copolymer latex is improved but its print gloss and adhesion strength are reduced.
  • the present inventors studied the method of using the molecular weight modifier in order to remove such an imbalance between blister resistance and print gloss, and have found that by using a special method of adding the modifier, the blister resistance and print gloss are improved and the adhesion strength can be fully retained even when the amount of gel as a whole remains the same.
  • a process for producing a copolymer latex for use as a binder in a paper coating composition by emulsion polymerization while monomers and a molecular weight modifier are continuously introduced into a reactor characterized in that
  • the molecular weight modifier is used in an amount of X o parts by weight (in which 0 ⁇ X o ⁇ 10) per 100 parts by weight of a monomeric mixture composed of (1) 20 to 50% by weight of an aliphatic conjugated diene monomer, (2) 15 to 70% by weight of a vinyl aromatic monomer, (3) 5 to 40% by weight of an alkyl ester of an ethylenically unsaturated carboxylic acid, (4) 0.5 to 10% by weight of an ethylenically unsaturated acid monomer, and (5) 0 to 30% by weight of a vinyl cyanide monomer, and
  • the molecular weight modifier is continuously added so that with the amount of the molecular weight modifier added per unit time at any time t in a time period of adding the monomers and the molecular weight modifier being X(t) parts by weight (per 100 parts by weight of the monomeric mixture added per unit time; on the same basis hereinafter), the following conditions are satisfied,
  • X(t) takes a minimum value of Xmin parts by weight and a maximum value of Xmax parts by weight within said time period of addition
  • the characteristic feature of the present invention is that the amount of the molecular weight modifier is continuously changed when a copolymer latex is produced by polymerizing the aforesaid monomeric mixture while continuously adding the monomeric mixture and molecular weight modifier into the reactor.
  • FIGS. 1 to 6 are graphs showing examples of the method of adding the molecular weight modifier in accordance with this invention.
  • FIGS. 7 to 15 graphs showing the behaviors of adding the molecular weight modifier during the production of copolymer latices in Example 1.
  • the ordinate represents the amount in parts by weight of the molecular weight modifier added and the abscissa, the addition time in hours.
  • the amount of the molecular weight modifier (the percentage based on the amount of the monomeric mixture simultaneously added) to be continuously introduced into the reactor should be changed with the lapse of time so that as shown in FIGS. 1 to 6, it has a maximum value (Xmax) and a minimum value (Xmin) between the start of addition and the end of addition.
  • the Xmin and Xmax may be at the time of starting and the time of ending respectively of the time period of addition (FIGS. 1 and 2), or may be reverse (FIGS. 3 and 4). Or both of X min and X max, or one of them, may be in an intermediate portion in the time period of addition (FIGS. 5 and 6).
  • copolymer latex in accordance with this invention obtained by using such a special method of adding the molecular weight modifier gives to a paper coating composition an effect of improving the balance between excellent blister resistance and print gloss which cannot be achieved by copolymer latices obtained by conventional methods, for example by a method in which all of the modifier is added at the start of polymerization, a method in which a part of the modifier is added at the start of polymerization and the remainder toward the end of polymerization, or a method in which the modifiers is uniformly added throughout the period of polymerization.
  • Examples of the aliphatic conjugated diene monomer (1) constituting the copolymer latex in accordance with this invention are 1,3-butadiene, 2-methyl-1,3-butadiene and 2-chloro-1,3-butadiene.
  • This monomer (1) is a component which gives a moderate degree of flexibility to the copolymer latex. If its amount is less than 20% by weight based on the entire monomeric mixture, the copolymer latex has an increased glass transition temperature and therefore poor film-formability, and is also reduced in adhesion strength. If its amount exceeds 50% by weight, the water resistance of the copolymer latex is reduced.
  • the amount of the monomer (1) is 25 to 40% by weight.
  • Examples of the vinyl aromatic monomer (2) are styrene, alpha-methylstyrene and vinyltoluene.
  • the monomer (2) gives a moderate degree of hardness to the copolymer latex, and water resistance of the coated paper which is important during offset printing. If the amount of the monomer (2) in the entire monomeric mixture is less than 15% by weight, the water resistance of the coated paper is insufficient. If it exceeds 75% by weight, the copolymer latex has poor film formability and reduced adhesion strength. Preferably, its amount is 30 to 60% by weight.
  • alkyl ester of an ethylenically unsaturated carboxylic acid (3) examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, monoethyl fumarate, diethyl fumarate, monoethyl itaconate, dimethyl itaconate, monobutyl fumarate, and monopropyl maleate.
  • the monomer (3) is a component which gives a moderate degree of hardness to the copolymer latex and improves ink transfer. If its amount is less than 5% based on the entire monomeric mixture, the ink transfer property of the coated paper is insufficient. If it exceeds 40% by weight, the copolymer latex has reduced water resistance and adhesion.
  • the preferred amount of the monomer (3) is 5 to 25% by weight.
  • Examples of the ethylenically unsaturated acid monomer (4) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid and maleic acid, and unsaturated sulfonic acids such as styrenesulfonic acid.
  • the monomer (4) is a component which increases the adhesion of the copolymer latex to pigments and raw paper and simultaneously improves the mechanical stability of the copolymer latex. If the amount of the monomer (4) is less than 0.5% by weight, it is difficult to achieve the purpose of using it. If it exceeds 10% by weight, the copolymer latex has alkali-thickening property. Hence, the copolymer latex has unsatisfactory handlability and reduced water resistance.
  • the preferred amount of the monomer (4) is 1 to 5% by weight.
  • Examples of the vinyl cyanide monomer (5) include acrylonitrile, alpha-chloroacrylonitrile, methacrylonitrile and alpha-ethylacrylonitrile.
  • the monomer (5) is a component which improves the gloss of coated paper. If it exceeds 30% by weight based on the entire monomeric mixture, the adhesion to pigments and raw paper and ink transfer property of the coated paper are markedly reduced.
  • Another monomer may be used in an amount of up to 10% by weight based on the entire monomeric mixture in addition to the monomers (1) to (5) mentioned above.
  • Examples include ethylenically unsaturated carboxylic acid amides and N-substituted products thereof, such as acrylamide, methacrylamide and N-methylolacrylamide; unsaturated alcohols such as allyl alcohol; and functional alkyl ester compounds such as beta-hydroxyethyl acrylate and glycidyl methacrylate.
  • the monomers must be added continuously to the polymerization system by various methods.
  • the monomeric mixture is continuously introduced into the reactor; or the monomeric mixture is divided into two or more monomeric mixtures having varied monomer compositions and the divided monomeric mixtures are continuously added to the reactor.
  • the known emulsion polymerization method may be followed.
  • the monomeric mixture is used after emulsifying it with an emulsifier.
  • the emulsifier examples include anionic surface-active agents such as sulfuric acid esters or higher alcohols, alkylbenzenesulfonic acid salts and aliphatic sulfonic acid salts; nonionic surface-active agents such as alkyl esters, alkylphenyl ethers and alkyl ethers of polyethylene glycols; and amphoteric surface-active agents such as betaine. These emulsifiers may be used singly or in combination. In view of the water resistance of the copolymer latex to be obtained, the amount of the emulsifier is desirably not more than 1% by weight.
  • polymerization initiators there may be used, for example, water-soluble initiators such as potassium persulfate and ammonium persulfate, redox initiators and oil-soluble initiators such as benzoyl peroxide and azobisisobutyronitrile.
  • molecular weight modifiers examples include mercaptans such as octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n-tetradecylmercaptan, t-tetradecylmercaptan, n-hexadecylmercaptan and t-hexadecylmercaptan; sulfides such as tetraethyl thiuram sulfide, dipentamethylenethiuram hexasulfide and diisopropylxanthogene disulfide; and alkyl halides such as carbon tetrachloride, methyl chloride, carbon tetrabromide and ethylene bromide. These modifiers may be used singly or in combination.
  • Pigments which can be used to prepare a paper coating composition by mixing it with the copolymer latex of this invention include, for example, mineral pigments such as clay, calcium carbonate, aluminium hydroxide, titanium white, barium sulfate, satin white and talc, and organic pigments such as polystyrene and phenolic resins. Clay, particularly kaolinite clay, is preferred.
  • the copolymer latex obtained by this invention may be used, if required, together with another binder, for example, water-soluble polymers such as starch, casein, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose and sodium alginate; and latices such as a styrene/butadiene copolymer latex, a methyl methacrylate/butadiene copolymer latex, a polyvinyl acetate latex and an acrylate copolymer latex.
  • water-soluble polymers such as starch, casein, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose and sodium alginate
  • latices such as a styrene/butadiene copolymer latex, a methyl methacrylate/butadiene copolymer latex, a polyvinyl acetate latex and an acrylate copolymer latex.
  • the copolymer latex of this invention may be used usually in an amount of 2 to 40% by weight based on the total amount (solids) of the pigment and binder.
  • the paper coating composition may further include a pigment dispersant, a viscosity adjusting agent, a water holding agent, a water-proofing agent, a dye, a fluorescent dye, a lubricant, a pH adjusting agent, a defoamer, a surface-active agent, an antiseptic agent, if required.
  • a tank equipped with a stirrer was charged with the following ingredients to form a monomer emulsion.
  • the inside of the autoclave was heated to 80° C., and the above monomer emulsion was continuously added to the autoclave uniformly over the course of 6 hours. Simultaneously, 1.0 part by weight in total of t-dodecylmercaptan was continuously introduced into the autoclave over the course of 6 hours so that the amount X(t) of dodecylmercaptan per 100 parts of the monomers added per unit time continuously changed as shown in FIGS. 7 to 12, or was continuously added at a constant rate (FIG. 13) or at two different rates (FIGS. 14 and 15).
  • the copolymer latices obtained are designated as latices A to F (invention) and latices G to I (comparison).
  • Copolymer latices were produced by polymerization while continuously adding emulsions in two steps as shown in Table 1. After the addition in the first step, the addition in the second step was immediately started. Otherwise, the same procedure as in Example 1 was repeated.
  • a paper coating composition of the following recipe was prepared by using each of the copolymer latices A to K.
  • composition was coated on a sheet of raw paper by a blade coater at a rate of 14 g/m 2 , and immediately then, dried in hot air at 130° C. for 20 seconds at a speed of 1 m/sec.
  • the coated paper was conditioned for one day at a temperature of 20° C. and a relative humidity of 65%, and supercalendered twice at a temperature of 60° C. and a linear pressure of 100 kg/cm to prepare a sample.
  • Offset ink (having a high tack) was printed on the sample five times using an RI tester (supplied by Akira Seisakusho). The degree of pick was observed visually, and rated by a 5-point method where point 5 means that the adhesion strength is sufficiently strong and point 1 means that the adhesion strength is quite weak.
  • test sample was prepared in accordance with TAPPI Standard T-526, and dipped for about 3 seconds in each of silicone oil baths kept at various temperatures. The sample was dried and observed for the oocurrence of blisters. By this procedure, the lowest temperature at which blisters formed was determined.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
US07/220,394 1984-08-31 1988-07-19 Process for producing copolymer latex Expired - Lifetime US4831078A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP59-182035 1984-08-31
JP59182035A JPS6163794A (ja) 1984-08-31 1984-08-31 紙塗被用組成物

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US06770060 Continuation 1985-08-28

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US (1) US4831078A (enrdf_load_stackoverflow)
JP (1) JPS6163794A (enrdf_load_stackoverflow)
DE (1) DE3531103C2 (enrdf_load_stackoverflow)
FR (1) FR2569704B1 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130368A (en) * 1989-10-16 1992-07-14 The B. F. Goodrich Company Colloidal polymeric compositions for fibrous substrate saturation
US5629047A (en) * 1990-08-06 1997-05-13 Gencorp Inc. Method of making functionalized styrene butadiene type latex binders
CN111253511A (zh) * 2020-01-19 2020-06-09 杭州龙驹合成材料有限公司 一种高强度造纸底涂胶乳及其生产工艺

Families Citing this family (12)

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JPS6312614A (ja) * 1986-07-02 1988-01-20 Asahi Chem Ind Co Ltd 共重合体ラテツクス及びこれを用いた接着剤
JP2605344B2 (ja) * 1987-05-29 1997-04-30 日本合成ゴム株式会社 紙塗被組成物
JPH01192897A (ja) * 1988-01-22 1989-08-02 Japan Synthetic Rubber Co Ltd グラビア印刷用紙塗工組成物
JPH01201599A (ja) * 1988-02-04 1989-08-14 Japan Synthetic Rubber Co Ltd グラビア印刷用塗工紙の製造方法
JP2555294B2 (ja) * 1989-06-30 1996-11-20 日本合成ゴム株式会社 紙塗被組成物
JP2615249B2 (ja) * 1990-06-07 1997-05-28 旭化成工業株式会社 ジエン系共重合体ラテックスの製造方法
JPH05171096A (ja) * 1991-12-20 1993-07-09 Asahi Chem Ind Co Ltd 顔料組成物
JP3283311B2 (ja) * 1992-12-25 2002-05-20 三井化学株式会社 紙塗工用組成物及び該組成物を塗工して得られる塗工紙
US5700852A (en) * 1994-04-06 1997-12-23 Japan Synthetic Rubber Co., Ltd. Paper coating composition
KR100335641B1 (ko) * 2000-02-21 2002-05-08 강석주 고속 인쇄용 도공지에 사용되는 고 접착력 라텍스의제조방법
EP2289991A1 (en) * 2009-08-26 2011-03-02 University Of Waterloo Nano-sized diene-based polymer latex particles
KR102365019B1 (ko) * 2014-03-27 2022-02-17 제온 코포레이션 니트릴기 함유 공중합체 고무, 가교성 고무 조성물 및 고무 가교물

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GB888503A (en) * 1959-09-14 1962-01-31 Goodrich Co B F Improvements in and relating to interpolymers
GB921798A (en) * 1960-04-28 1963-03-27 Bayer Ag Aqueous copolymer emulsions and coatings and impregnations made therefrom
US3847032A (en) * 1972-05-11 1974-11-12 H Moser Torque equalizing drive
DE2332637A1 (de) * 1973-06-27 1975-01-23 Basf Ag Verfahren zur herstellung von waessrigen butadiencopolymerisat-dispersionen
DE2437365A1 (de) * 1973-08-03 1975-02-13 Int Synthetic Rubber Verfahren zur herstellung von latices
JPS5094034A (enrdf_load_stackoverflow) * 1973-12-24 1975-07-26
US3970629A (en) * 1972-08-07 1976-07-20 Sumitomo Naugatuck Co., Ltd. Composition for paper coating
US4001163A (en) * 1974-04-17 1977-01-04 Bayer Aktiengesellschaft Styrene-butadiene copolymer latices containing carboxyl groups
DD134771A1 (de) * 1978-02-08 1979-03-21 Frans Steffers Verfahren zur herstellung von carboxylierten butadiencopolymerisatlatices
JPS5458789A (en) * 1977-10-19 1979-05-11 Nippon Zeon Co Ltd Novel conjugated diolefin copolymer latex
DD146612A1 (de) * 1979-10-08 1981-02-18 Frans Steffers Verfahren zur herstellung von carboxyllatices mit verbesserten gebrauchswerteigenschaften
JPS57153012A (en) * 1981-03-19 1982-09-21 Sumitomo Naugatuck Co Ltd Production of copolymer latex having excellent adhesiveness
JPS57153011A (en) * 1981-03-19 1982-09-21 Sumitomo Naugatuck Co Ltd Production of copolymer latex
JPS57180617A (en) * 1981-05-01 1982-11-06 Japan Synthetic Rubber Co Ltd Copolymer latex for chipping-resistant paint
US4358403A (en) * 1980-09-03 1982-11-09 Basf Aktiengesellschaft Aqueous low-emulsifier dispersions of butadiene-styrene emulsion copolymers containing carboxyl groups
GB2101615A (en) * 1981-07-02 1983-01-19 Polysar Int Sa Hard shell soft core latex
US4429074A (en) * 1978-12-28 1984-01-31 Sumitomo Naugatuck Co., Ltd. Paper coating composition and its production

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AU474688B2 (en) * 1973-08-15 1975-02-20 Sumitomo Naugatuck Co. Ltd. Copolymer latex and paper coating composition thereof
DE2842719A1 (de) * 1978-09-30 1980-04-10 Basf Ag Verfahren zur herstellung von waessrigen polyacrylat-dispersionen mit verbessertem fliessverhalten
JPS5891707A (ja) * 1981-11-27 1983-05-31 Dainippon Ink & Chem Inc ラテックスポリマ−の製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB888503A (en) * 1959-09-14 1962-01-31 Goodrich Co B F Improvements in and relating to interpolymers
GB921798A (en) * 1960-04-28 1963-03-27 Bayer Ag Aqueous copolymer emulsions and coatings and impregnations made therefrom
US3847032A (en) * 1972-05-11 1974-11-12 H Moser Torque equalizing drive
US3970629A (en) * 1972-08-07 1976-07-20 Sumitomo Naugatuck Co., Ltd. Composition for paper coating
DE2332637A1 (de) * 1973-06-27 1975-01-23 Basf Ag Verfahren zur herstellung von waessrigen butadiencopolymerisat-dispersionen
DE2437365A1 (de) * 1973-08-03 1975-02-13 Int Synthetic Rubber Verfahren zur herstellung von latices
US3966661A (en) * 1973-08-03 1976-06-29 The International Synthetic Rubber Company, Limited Preparation of latices
JPS5094034A (enrdf_load_stackoverflow) * 1973-12-24 1975-07-26
US4001163A (en) * 1974-04-17 1977-01-04 Bayer Aktiengesellschaft Styrene-butadiene copolymer latices containing carboxyl groups
JPS5458789A (en) * 1977-10-19 1979-05-11 Nippon Zeon Co Ltd Novel conjugated diolefin copolymer latex
DD134771A1 (de) * 1978-02-08 1979-03-21 Frans Steffers Verfahren zur herstellung von carboxylierten butadiencopolymerisatlatices
US4429074A (en) * 1978-12-28 1984-01-31 Sumitomo Naugatuck Co., Ltd. Paper coating composition and its production
DD146612A1 (de) * 1979-10-08 1981-02-18 Frans Steffers Verfahren zur herstellung von carboxyllatices mit verbesserten gebrauchswerteigenschaften
US4358403A (en) * 1980-09-03 1982-11-09 Basf Aktiengesellschaft Aqueous low-emulsifier dispersions of butadiene-styrene emulsion copolymers containing carboxyl groups
JPS57153012A (en) * 1981-03-19 1982-09-21 Sumitomo Naugatuck Co Ltd Production of copolymer latex having excellent adhesiveness
JPS57153011A (en) * 1981-03-19 1982-09-21 Sumitomo Naugatuck Co Ltd Production of copolymer latex
JPS57180617A (en) * 1981-05-01 1982-11-06 Japan Synthetic Rubber Co Ltd Copolymer latex for chipping-resistant paint
GB2101615A (en) * 1981-07-02 1983-01-19 Polysar Int Sa Hard shell soft core latex

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130368A (en) * 1989-10-16 1992-07-14 The B. F. Goodrich Company Colloidal polymeric compositions for fibrous substrate saturation
US5629047A (en) * 1990-08-06 1997-05-13 Gencorp Inc. Method of making functionalized styrene butadiene type latex binders
CN111253511A (zh) * 2020-01-19 2020-06-09 杭州龙驹合成材料有限公司 一种高强度造纸底涂胶乳及其生产工艺
CN111253511B (zh) * 2020-01-19 2023-01-03 杭州龙驹合成材料有限公司 一种高强度造纸底涂胶乳及其生产工艺

Also Published As

Publication number Publication date
FR2569704B1 (fr) 1988-11-04
FR2569704A1 (fr) 1986-03-07
JPS6163794A (ja) 1986-04-01
JPH0342360B2 (enrdf_load_stackoverflow) 1991-06-26
DE3531103A1 (de) 1986-04-10
DE3531103C2 (de) 1994-09-08

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